Alpha-cyano-1 3-dithiolane - delta 2 a - thionoacetic acid derivatives and process for preparing the same

ABSTRACT

HALOCYANOETHYLENE REACTS WITH ALKYLENE TRITHIOCARBONATES TO FORM A-CYANO-1,3-DITHIOLANE-$2,A-THIONACETYL HALIDES AND A-CYANO-1,3-DITHIANE-$2,A-THIONACETYL HALIDES, FURTHER PRODUCTS CAN BE MADE BY INTERCHANGE OF THE HALOGEN OR BY REACTING THE HALOGEN WITH AN ACTIVE HYDROGEN COMPOUND SUCH AS AN ALCOHL, THIOL OR AMINE. THE PRODUCTS ARE USEFUL AS DYESTUFFS FOR ACETATE, ACRYLIC AND POLYAMIDE FIBERS.

United States Patent a-CYANO-LS-DITHIOLANE A THIONOACETIC ACID DERIVATIVES AND PROCESS FOR PRE- PARING THE SAME Brian Russ OConnor, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del. No Drawing. Filed Aug. 13, 1968, Ser. No. 752,131

Int. Cl. C07d 71/00, 73/00 U.S. Cl. 260-327 M 3 Claims ABSTRACT OF THE DISCLOSURE H'alocyanoethylene reacts with alkylene trithiocarbonates to form a-cyano-l,3-dithiolane-A "-thionacetyl h-alides'and a-cyano-l,3-dithiane-A "-thionacetyl halides. Further products can be made by interchange of the halogen or by reacting the halogen with an active hydrogen compound such as an alcohol, thiol or amine. The products are useful as dyestuffs for acetate, acrylic and polyamide fibers.

FIELD OF THE INVENTION This invention is in the field of novel heterocyclic dyestufis and especially relates to new 1,3-dithiolanes and to a new process for preparing. the 1,3-dithiolanes.

BACKGROUND OF THE INVENTION 'It is known that certain alkylene trithiocarbonates react with dimethyl acetylenedicarboxylate to form substituted 1,3-dithiolane-2-thiones and the olefin corresponding to the alkylene portion of the alkylene trithiocarbonate (D. B. J. Easton and D. Leaver, Chem. Communications, 1965, 585). For example:

' S t R 140C. =s n-000cm R s d-oooon,-

s on oooj orr ooo It has now been discovered that a facile reaction occurs between alkylene trithiocarbonates and halocyanoacetylene to yield surprising and useful products.

SUMMARY OF THE INVENTION The general formula of the products of this invention is:

3,637,749 Patented Jan. 25, 1972 R groups can be alike or different. In addition R can be hydrogen.

The halo compounds (except fluorine) can be prepared by reacting a halocyanoacetylene having the formula XECCN with an alkylene trithiocarbonate having the formula in an inert 'aprotic organic solvent at a temperature of 0 to C., to obtain DETAILED DESCRIPTION OF THE INVENTION The alkylene trithiocarbonates used in the practice of this invention are 1,3-dithiolane-2-thiones and 1,3-dithian- 2-thiones having only hydrocarbyl substituents on the 4,5 or 4,5,6 carbons, respectively. These are described in D. S. Breslow and H. Skolnik, Multisulfur and Sulfur-Oxygen 5- and -membered Heterocycles, Interscience, New York, Part 1, pp. 530-546, 1960, The preferred reactants are the 1,3-dithiolane-2-thiones as defined above. 4-aryl- 1,3-dithiolane-2-thiones are preferred as giving the deepest color for dyes. The halocyanoacetylenes in which halogen is chlorine, bromine or iodine which form the other reactant in the initial step are known compounds.

The novel reaction of halocyanoacetylenes with alkylene trithiocarbonates to form a-cyano-l,3-dithiolane- A -thiOnacetyl halide is carried out by stirring the reactants in a suitable inert aprotic solvent at 0 to 80 C. for 4 to 24 hours or longer. Preferably, this reaction is allowed to procede at from ambient temperatures to slightly elevated temperatures, e.g., at from about 20- 50 C.

Suitable inert aprotic solvents include benzene, toluene, Xylenes, tetrahydrofuran, carbon disulfide, chloroform, methylene chloride, acetonitrile, acetone, methyl ethyl ketone and chlorofiuorohydrocarbons that boil in a convenient range, e.g., 45-100" C.

Stirring or shaking the reaction mixture, while not essential, is desirable in order to elfect intimate contact of the reactants and thus increase the speed of reaction.

The reaction requires one mole each of the halocyanoacetylene and alkylene trithiocarbonate and it is therefore prefer-red to employ the reactants in an approximate 1:1 mole ratio. However, it is possible to react the compounds in any ratio, the amount of product being limited by the reactant in deficiency.

The additional products of this invention in which X=, -OR, -SR, and NRR' are prepared by a simple metathetical reaction of the u-cyano-1,3-dithiolane-A thionoacetyl halide. The higher or somewhat hindered alcohols, thiols, or amines may react slowly and it may be desired to warm the reaction mixture. It usually suffices to warm to steam bath temperatures, i.e., ca. 80 C.; preferably, the reaction is elTected at 2050 C. In these reactions an excess of the alcohol, thiol or amine is conveniently used as solvent though other solvents may be used.

Exchange of the halogen in a-cyano-1,3-dithiolane-A thionoacetyl halides is conveniently carried out as in Example 3 by refluxing with the salt of another halide. This exchange is particularly useful to exchange of the halogen in the easily prepared int-cyano-1,3-dithiolane-A '-thionoacetyl chloride or bromide with a metallic fluoride to make the otherwise unavailable fluoride compound.

UTILITY Compounds of this invention are useful in dyeing cellulose triacetate, nylon and, surprisingly, acrylic fibers, as represented by Zephran and Creslan. These dyes are particularly adaptable to the well-known method of disperse dyeing. A convenient procedure is as follows:

A dye bath is prepared by dissolving 1 part of dye in the minimum amount (generally 5-15 parts) of good solvent such as acetone, glycol, acetic acid, methyl ethyl ketone, and dimethylformamide. The crude dye solution is poured into a vessel containing 400 parts of rapidly stirred Water. Alternatively, it is convenient, and often superior results are obtained, to pour the dye solution into a dilute aqueous solution of 1 part of a sulfonated lignin dispersant (Marasperse, Marathon Corporation), in 400 parts of water. Under these conditions the dye bath is usually colorless and in no event is the bath deep colored. Skeins of fiber or swatches of fabric are immersed in the dye bath and the mixture heated on a steam bath for about 1 hour. The skeins or swatches are stirred occasionally to minimize uneven dyeing. The dyed product is removed from the bath, washed with soap and water, rinsed thoroughly, and dried.

This invention is further illustrated by the following specific examples which should not, however, be construed as fully delineating the scope thereof. In these examples, parts are given by weight unless otherwise specified.

EXAMPLE 1 To a stirred solution of 6.5 g. (0.05 mole) of bromocyanoacetylene in 100 ml. of exylene was added in portions 6.8 g. (0.05 mole) of ethylene trithiocarbonate. The mixture was stirred for 24 hours at 25-35 C. and the product collected as 12.0 g. of a red-violet crystalline solid, M.P. 126-140, C. (dec.).

Analysis.Calcd. for C H BrNS (percent): C, 27.07; H, 152; N, 5.27; S, 36.13; Br, 30.02. Found (percent): C, 27.47, 27.25; H, 1.94, 1.63; N, 5.27, 5.27.

Recrystallization of 1.0 g. of the material from 25 ml. of hot benzene yielded 0.5 g. of a-cyano-1,3,-dithiolane-A -thioacetyl bromide brilliant red-violet needles, M.P. 126 C. (dec.); UV max. (CH CN), 242 m (6 20,000), 266 III/.0 (6400), 294 m (3300), 330 m (3860), 400 m (19,200), and 520 m (130); IR (KBr) 2200 cm.- (m.), 1355 cm. (s.), and 1325 cm.- (s.); NMR (CH CI 6 3.67 (s.).

Arzalysis.-Found (percent): C, 27.16; H, 1.43; N, 5.27; S, 35.51; Br, 30.10. M.W. Calcd.: 266. Found: 284 (cryoscopic in benzene).

EXAMPLE 2 A solution of 1.3 g. (0.01 mole) of bromocyanoacetylene and 2.1 g. (0.01 mole) of 4-phenyl-1,3-dithiolane-Z-thione in 25 ml. of benzene was stirred at 25 C.

for 24 hours and 2.2 g. of nearly pure a-cyano-4-phenyl- 1,3-dithiolane-A -thioacetyl bromide was collected as a red-violet solid, M.P. 125126 C. (dec.). An analytical sample, obtained by crystallizing 1.9 g. of the product from 60 ml. of 50:50 hexane:benzene, had M.P. 125- 126 C. (dec.); UV max. (CH CN) 244 m (6 24,700), 265 m sh., 295 II1,u (e 3750), 334 m (6 3860), 408 m r (6 20,150, and 522 my (6 126); IR (KBr) 2205 cm. (m.), 1390 cm.- (s.), and 1308 cm.- (s.); NMR (CDCl 6 8.5 (s.,5), 6 5.38 (t.,l), 6 3.81-4.04 (m.,2).

Analysis.-Calcd. for C H NS Br (percent): C, 42.10; H, 2.36; N, 4.09; Br, 23.35; S, 28.11. Found (percent): C, 42.16; H, 2.21; N, 3.85; Br, 23.32; S, 28.20. M.W: Calcd.: 342. Found: 347 (Fp. in benzene).

EXAMPLE 3 A slurry of 2.6 g. (0.01 mole) of u-cyano-1,3-dithiolane-A -thioacetyl bromide and 6.0 g. (0.10 mole) of potassium fluoride in 50 ml. of acetonitrile was refluxed under nitrogen for 15 hours. The insoluble solids were filtered and the filtrate concentrated to yield 1.58 g. of crude product, M.P. -101 C. The crude product was purified by sublimation at C. (0.1 mm.) to yield u-cyano-1,3-dithiolane-A -thioacetyl fluoride, a bright yellow-orange solid, M.P. 105.5107.5 C. UV max. (CH CN) 219 111,44 (e 9300), 241 111,11. (6 11,600), 260 m sh., 317 me (e 5550), and 383 m (6 18,200); IR (KBr) 2205 cm.- (m.), 1775 cm.- (w.), 1420 cm.- (s.), and 1120 cm.- (s.); H NMR (CD CN) 6 3.87 (s.); F NMR (CH CN) --57.7 ppm. from F-ll (s.).

Analysis.Calcd. for C H NS F (percent): C, 35.10; H, 1.97; N, 6.82; F, 9.25. Found (percent): C, 35.16, H, 1.84; N, 7.02; F. 9.35.

EXAMPLE 4 A slurry of 1.0 g. (0.0038 mole) of a-cyano-l,3- dithiolane-A -thioacetyl bromide in 40 ml. of ethyl alcohol was stirred at 25 C. for 24 hours. Eethyl u-cyano- 1,3-dithiolane-A -thionoacetate was collected as 0.65 g. of a yellow solid, M.P. 133-134" C.; UV max. (CH CN) 246 m z (612,000), 278 m (6 4350), 300 mg (6 5400), and 360 mg (e 18,400); IR (KBr) 2200 cm. (m.) and 1445 cm- (s.); NMR (CD01 6 4.62 (q., 2, J=7 Hz), 51.49 (t., 3, J=7 Hz.), 6 3.63 (s., 4).

Analysis.-Calcd. for C H NOS (percent): C,'4l.52; H, 3.93; N, 6.06; S, 41.57. Found (percent): C, 41.42; H, 3.94; N, 6.13; S, 41.88. M.W. calcd: 236. Found 231 (Fp in benzene).

EXAMPLE 5 (A) A slurry of 2.6 g. (0.01 mole) of a-cyano-1,3-dithiolane-A -thioacetyl bromide in 75 ml. of methanol was stirred 12 hours at 25 C. Methyl a-cyano-1,3-dithiolane-A -thionoacetate was collected as 2.1 g. of a light brown solid, M.P. 133-135 C. (dec.).

Analysis.Calcd. for C7H7NS3O (percent): C, 38.68; H, 3.25; N, 6.45. Found (percent): C, 38.38; H, 3.15; N, 6.46.

(B) A slurry of the compound in hot water dyed acetate, Arnel cellulose triacetate fiber, Creslan acrylic fiber, nylon, and Zephran acrylic fiber yellow.

EXAMPLE 6 A slurry of 1.0 g. (0.0029 mole) of a-cyano-4-phenyl- 1,3-dithiolane-A '"-thioacetyl bromide in 30 ml. of ethanol was stirred at 25 C. overnight and 0.6 g. of ethyl a-cyano- 4-phenyl-1,3-dithiolane-A "-thioacetate, 133-134 C. (dec.) was collected; UV max. (CH CN) 247 m (a 16,- 300), 305 m (6 5500), 363 my. (6 19,000); IR (KBr) 2202 cm.- (m.), 1455 cm.- (s.), NMR (CDCI 6 8.42 (m., 5), 6 5.18 (t., 1, J=8.5 Hz.); 6 4.57 (q., 2, J=7 Hz.); 6 3.71 (d., 2, J=8.5 Hz.), 51.41 (t., 3, J=7 Hz.).

Analysis.-Calcd. for C H NOS (percent): C, 54.66; H, 4.26; N, 4.56; S, 31.28. Found (percent): C, 54.82; H, 3.94; N, 4.51; S, 31.64. 1

(S EXAMPLE 7 (A) To a solution of 5.3 g. (0.02 mole) of a-cyano-1,3- dithiolane-A -thioacetyl bromide in 100 ml. of tetrahydro- Trituration of the oil with ether yielded 4.0 g. of crude N,N-diethyl a-cyano-1,3-dithiolane A thioacetamide, 'MaP. 65-69 C. Crystallization of 2 g. from 100 ml. of 1:1 ether-benzene yielded 0.6 g. of an analytical sample, M.P.

furan was added 5.5 g. (0.061 mole) of aniline. The mix- 5 43 3,; UX mam (CHECN) 2 (E 13, 00 305 ture was stirred for several hours at 25 C. then the ani- (6 14,400), 7 (8 IR (KBr) 5 -1 (W) line hydrobromide collected and the filtrate concentrated d 1515 m (3.); NMR (CDCl,-,) 6 3.85 (q., 4, 1:7 to yield 5.5 g. of crude N-phenyl a-cyano-1,3-dithiolane- 5 130 (a, 6, 1:7 Hz), 6 3.58 (s., 4). A '-thioacetamide, M.P. 153-160 C. Two crystallizations l i c 1 d for C H N S (percent): C, 46.47; from benzene yielded bright yellow crystals, 1725- 10 H, 5.46; N, 10.84; s, 37.22. Found (percent): 0, 46.33; H, UV Q 243 11114 1 292 5.40; N, 10.91. M.W. Calcd.: 258. Found: 270 (Fp in III/.1, (a 8,400), 342 mu (17,400), and 435 m sh. (e 550); benzene) IR (KBr) 3,200 cmr (m.), 2,198 cm. (m.), 1,595 cm." (w.), 1,520 cm. (m.), 1,470 cm:- (s.), and 1,455 EXAMPLE 1O NMR a) 5 5 5 Anhydrous dimethylamine was bubbled through a stirred y for 12 10 2 3 (P 51-77; solution of 5.3 g. (0.02 mole of u-cyano-1,3-dithiolane- 353; 1005- Found (P 3 H, i A -thioacetyl bromide in 175 ml. of tetrahydrofuran until h the red color was completely discharged. The dimethyl- Shifty of the compound hot Water with 2 drop? amine hyrobromide was collected (2.35 g.) and the filtrate of acetic acid added dyed acetate, Arnel cellulose tr1- comm/[rated under reduced pressure to yield 45 f acetate fiber, Creslan acrylic fiber, nylon, and Zephran crude NNdimethYl -1 2. i acryhc fi y amide. Crystallization of 1.0 g. from 75 ml. of 70:30 EXAMPLE 8 benzene-hexane yielded 0.7 g. of bright yellow needles, M.P. l46l48 C.; UV max. (CH CN) 208 mu (5 8250), (A) Anhydrous methylamine was bubbled through a 260 m (6 12,800), 307 III/1. (14,000), and 390 m (6 stirred solution of 5.3 g. (0.02 mole) of ot-cyano-l,3-di- 1150); IR (KBr) 2205 cm. (m.), 1530 om.- (s.), and thiolane-A thioacetyl bromide in 125 ml. of tetrahydro- 1500 cm, (5,); NMR (CH CI 5 3.59 (s., 4) and 6 3.39 furan until the red color was completely discharged. The 6), insoluble yellow solid which had formed was collected Anglysis calcd for C H N S C, 4156; (3.82 g.) and extracted with 40 ml. of distilled water. The H, 4.37; N, 12.16; S, 41.75. Found (percent): C, 41.51; water-insoluble p y y -mi i H, 4.54; N, 12.17; s, 41.81. M.W. Calcd.: 230. Found: A -thioacetamide, was obtained as 1.63 g. of a yellow 233 (Fp in DMSO). solid, M.P. 218-220" C. The tetrahydrofuran solution was concentrated and yielded 2.6 g. of a yellow-orange solid, EXAMPLE 11 M.P. 198212 C. An analytical sample (0.62 g., M.P. 219221 C.) was obtained by crystallizing 1.0 g. of the A 5011111011 0f 111016) of tr0116311119116- crude product from 110 ml. of benzene; IR (KBr) 3300 trithiocarbonate and 4.3 g. (0.033 mole) of bromocyanocmr (m.), 2200 cm.- (m.), 1535 cm. (m.), 1480 acetylene in 80 ml. of benzene was stirred at 25 C., and cm.** (s.); NMR (CD SOCD )1 8.45 (m., 1), 6 3.72 (s., after a few minutes brilliant crystals of a-cyano-1,3-dithio- 4), 6 3.12 (d., 3, 1:45 Hz.). lane-A -thionoacetyl bromide appeared. After standing A yfor '1 8 2 3 (P C, overnight, the crystalline product partly decomposed and H, N, S, 44.46. FOund (Percent): C, was no longer crystalline I H, 3.92; N, 12.97; S, 44.54. M.W. ca1cd.: 216. Found: 209 (B) The above Synthesis was repeated except f use P DMSO)- of additional benzene (100 ml. total) and protection of the 2 A Shiny of the cqmPound water l reaction mixture by an atmosphere of nitrogen. After 24 tate Amel cenlllose f g i acryhc hours reaction time, 4.0 g. of dark crystalline ot-cyano-l,3- fiber nylon and Zephran any 10 er ye dithiolane-A "thionoacetyl bromide was collected by filtration and dried in a desiccator.

EXAMPLE 9 The following table further exemplifies the prepara- To a solution of 5.3 g. (0.02 mole) of a-cyano-1,3-dition of oc-cyano-4-, and/or S-substituted-l,3-dithi01ane-A thiolane-A --thioacety1 bromide in ml. of tetrahydrothionoacetyl halides. When the alkylene trithiocarbonates furan was added 4.4 g. (0.06 mole) of diethylamine. After of column 1 are reacted, as described in the preceding a few hours 2.9 g. of diethylamine hydrobromide was colexamples, with the halocyanoacetylene of column 2, the lected and the filtrate concentrated to a yellow-brown oil. product of column 3 is obtained.

TABLE I Halocyanoacetylene; Alkylene trithioearbonate XO=CCN, X= Product 4-methyl-l,3-dithiolane-2-thione Br a-Gyano-4-methy1-1,3-dithio1ane-A ---thionoacety1 bromide.

4,5-dimethyl-l,3-ditl1iolane-2-thione Br 4,4-dlmethyl-1,3-dithio1ane-2-thione C1 4-ethy1-1,3-d1thiolane-2-thione Cl 4-n-butyl-1,3-dithiolane-2-thione Cl, (Br) 4-n-octyl-1,3-dithiolane-2-thione Cl, (Br) 4-n-hexyl-4-ethyl-1,3-d1th1olane-2-thione Br 4-p-tolyl-1,3-dithioiane2-thione Br 4-(2,4-xylyl) -1,3-dithiolane-2-thione -Br 4-(2ethylphenyl) l ,3-dithiolane-2-thione Br 4,5diphenyl-l,3dithiolane-2-thione Cl, (Br) 4-methyl-4-phenyl-l,3-dithiolane-2-thione. Cl, (Br) aCyano-hddimethyl-l,3-dithiolane-A -thionoacetyl bromide. a-Oyano-4A-dimethyl-1,3-dithiolane-A thionoacetyl chloride. a-Gyano-4-ethyl-1,3-dithiolane-M -thionoacetyl chloride. a-Cyano4-n-butyil,S-dithiolane-A thionoacetyl chloride (bromide). a-Gyano-4-n-o'ety1-1,3-dithiolane-A '-thiloaeetyl chloride (bromide). a-Cyano-4-nhexyl-4-ethyl-1,3-dithiolane-A -thionoacetyl bromide. a-Cyano4-p-toIyl-1,3-dithiolane-A "-thionoacetyl bromide. a-Cyanot-(2,4-xy1yl)l,3-dithiolane-A -thionoacetyl bromide. a-Cyano-t-(w-ethylphenyD-l,3-dithiolane-A --thionoacetyl bromide. aCyano4,fi-diphenyl-lfi dithiolane-A -thionoacetyl chloride (bromide). a-Cyano-4-methyl-4phenyl-1,3-dithiolane-A --thionoacetyi chloride (bromide).

The following table further exemplifies the preparation of a-cyano-4-, and/or S-substituted-l,3-dithiolane-A 3. Process of making a compound having the formula:

thionoacetates, -dithioacetates, and thioacetamides. When S the reactant from column 1 is stirred or warmed with the 1 (3:0 reactant from column 2, the product in column 3 is btained.

TABLE II a-CYZlI-4-, and/or Bsubstitutcd 1,3 iithiolane- A -thionoacetyl halide Alcohol, thiol or 4 4 5 5' Halogen amine Product OH; H H H Br n-Octyl alcohol n-O ctyl a-eyano4-methyl-l 3-dithlolano-A -thionoacetate. CH; H OH; H Br 1octanthiol n-Octyl a-cyano-4,5-dimethyl-1,3-dithiolane-A -dithioacetate. C H H H H Br Phenol Phenyi a-cyano-4-phenyl-1,3-dithiolane-A -thionoacetate. C ll H C611 H Br p-Cresol p-Cresyl a-cyano-4,5-diphenyl-1,3-dithiolane-A -thionoacetate. CIL'QCQH H H H Br Thiophenol. Phenyla-cyano-4-p-tolyl-1,3-dithiolane-A --dithioacetate. CH OH; H H Br 2,4-xyieno1. 2,4-xyiyla-eyano4A-dimethyl-1,3-dithiolane-N-"-thionoacetate. CH; OH; H H Br Ethanethiol" Ethyl Q-cyanQAA-dimethyl-IB-dithiolane'A --dithioacetate. 6 H; H H H Br N-methylanilme N-methyl-N-phenyla-cyano4-pheny11,3-dithlolanc-A" -thioacctamido. C H H H H Br 2,4-Xylidine N-(2,4)-xy1yl a-cyano-4-phenyl-1,3-dithiolanc-A -thioacetamide. 0 11 H H H Br Hexylamine N-n-hexyl a-eyano-4-phenyl-1,3-dithiolane-A --thioacetamide. 04H; H H H Br Oc ylamine N-octyl a-eyano-4-nbutyl-1,B-dithiolane-A -thioacetamide. CQH5 H H H Br B-Phenethyl alcohol. B-Phenethyl aeyano--phenyl-l,3-(iithiolane-A -thionoacetate. 0 H; H H H Br Benzyl alcoho1 Benzyl a-cyano4-phenyl-1,3 iithiolane-A -"-thionoacetate. C H H H H Br Benzyl mercaptanm Benzyl a-eyano-4-phenyl-1,34lithiolane-A -dithioacetate.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that this invention is not limited to the specific embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound having the formula wherein Y is halogen, --OR', -SR' or NRR R is hydrocarbyl of up to 8 carbon atoms and R is hydrocarbyl of up to 8 carbon atoms or hydrogen, said hydrocarbyl groups being alkyl or aryl groups.

2. A compound having the formula C-Br S wherein n is 2 or 3, and R is H or a hydrocarbyl of up to 8 carbon atoms, said hydrocarbyl group being alkyl or aryl groups.

in which n is 2 or 3, R is hydrogen or hydrocarbyl of up to 8 carbon atoms, said hydrocarbyl group being an alkyl or an aryl group, and X is chlorine, bromine or iodine, which comprises reacting a compound having the formula Gompper et al., CA. 58; 9067-8 (April 1963).

Mayer et al., CA. 62: 131401 (May 1965).

Lowy et al., Intro. Org. Chem. (New York, 1945), pp. 213-5.

HENRY R. JILES, Primary Examiner C. M. SHURKO, Assistant Examiner US. Cl. X.R. 8178 R, 179 

